WO2005001873A1 - Ecran plasma - Google Patents

Ecran plasma Download PDF

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Publication number
WO2005001873A1
WO2005001873A1 PCT/JP2004/009483 JP2004009483W WO2005001873A1 WO 2005001873 A1 WO2005001873 A1 WO 2005001873A1 JP 2004009483 W JP2004009483 W JP 2004009483W WO 2005001873 A1 WO2005001873 A1 WO 2005001873A1
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WIPO (PCT)
Prior art keywords
phosphor
plasma display
green
general formula
discharge
Prior art date
Application number
PCT/JP2004/009483
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English (en)
Japanese (ja)
Inventor
Yoshiki Tanaka
Masaki Aoki
Kazuhiko Sugimoto
Yuichiro Miyamae
Junichi Hibino
Hiroshi Setoguchi
Keiji Horikawa
Original Assignee
Matsushita Electric Industrial Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by Matsushita Electric Industrial Co., Ltd. filed Critical Matsushita Electric Industrial Co., Ltd.
Priority to EP04746952A priority Critical patent/EP1655757A4/fr
Priority to US10/534,398 priority patent/US7268492B2/en
Priority to CN2004800017914A priority patent/CN1723522B/zh
Publication of WO2005001873A1 publication Critical patent/WO2005001873A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7706—Aluminates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7715—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing cerium
    • C09K11/7721—Aluminates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7734—Aluminates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7777—Phosphates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/778—Borates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/7784—Chalcogenides
    • C09K11/7787—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J11/00—Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
    • H01J11/10—AC-PDPs with at least one main electrode being out of contact with the plasma
    • H01J11/12—AC-PDPs with at least one main electrode being out of contact with the plasma with main electrodes provided on both sides of the discharge space
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J11/00—Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
    • H01J11/20—Constructional details
    • H01J11/34—Vessels, containers or parts thereof, e.g. substrates
    • H01J11/42—Fluorescent layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2211/00—Plasma display panels with alternate current induction of the discharge, e.g. AC-PDPs
    • H01J2211/20—Constructional details
    • H01J2211/34—Vessels, containers or parts thereof, e.g. substrates
    • H01J2211/42—Fluorescent layers

Definitions

  • the present invention relates to a plasma display device used for displaying an image such as a television.
  • a display device using a plasma display panel (hereinafter referred to as a PDP or panel) is a power supply capable of realizing a large, thin, and lightweight. It is attracting attention as a display device.
  • PDPs perform full-color display by additively mixing the so-called three primary colors (red, green, and blue).
  • the PDP is provided with a phosphor layer that emits each of the three primary colors red (R), green (G), and blue (B).
  • Phosphor particles are excited by ultraviolet rays generated in the discharge cells of the PDP to generate visible light of each color.
  • each of these phosphors may be produced by mixing a predetermined raw material and then firing at a high temperature of 100 ° C. or more to perform a solid-phase reaction. It is disclosed in non-patent literature, such as the Phosphor Handbook (P219, 225 Ohm).
  • Zn 2 Si 0 4 : Mn which is used particularly in green, is covered with Si 0 2 , so that it is very easy to adsorb gas. That is, Zn 2 Si 0 4 : Mn is water (H 2 0), carbon monoxide (CO), carbon dioxide (C 0 2 ), or hydrocarbon gas (C x H 2 ) which is a decomposition product of organic binders. y ) is adsorbed in large quantities. They are gasified in the aging process after the panel is sealed, released into the panel and adsorbed on the surface of MgO, leading to deterioration of discharge characteristics.
  • these gases is a blue phosphor B aMg A 1 10 O 17: E u or green phosphor in which Z n 2 S I_ ⁇ 4: causing a surface reaction adsorbed on the surface of the Mn.
  • a green phosphor surface is negatively charged Z n 2 S i 0 4: Mn and, positively charged green
  • L a P 0 4: T b also because it has a P 0 4 in the crystal system, H 2 0 and C x H y gas adsorption ease Les therefore a, H 2 0 during the aging of the panel process and C x H y is released in the panel, these gases react chemically with the surface of the phosphor, the luminance degradation at prolonged panel lighting increases. If the brightness of blue or green is degraded, the color temperature will drop when the entire screen is displayed in white, and the screen will become yellowish, causing color shift of the panel.
  • the present invention has been made in view of such problems, as well as to the charging Te to base positive (+), H 2 0, CO, less green fluorescence of adsorption or reaction of C 0 2 or C x H y It is an object to provide a plasma display device having a body. Disclosure of the invention
  • Mn x is L a, any one of a C e
  • MM g Bok X A 1 M O l9 having a site crystalline structure: Mn x (M is, L a C e, whichever is one) and, yttrium port rate or yttrium aluminate of the general formula (Y a - y G .
  • FIG. 1 is a plan view showing a state in which a front glass substrate of a PDP used in a plasma display device according to an embodiment of the present invention is removed.
  • FIG. 2 is a perspective view showing the structure of the image display area of the PDP.
  • FIG. 3 is a block diagram of the plasma display device according to the embodiment of the present invention.
  • FIG. 4 is a cross-sectional view showing the structure of a PDP image display area used in the plasma display device according to the embodiment of the present invention.
  • FIG. 5 is a schematic configuration diagram of an ink coating apparatus used for forming a phosphor layer of the PDP.
  • FIG. 1 is a plan view showing a state where a front glass substrate of a PDP used in a plasma display device according to an embodiment of the present invention is removed
  • FIG. 2 is a perspective view showing a structure of an image display area of the PDP.
  • the number of display electrode groups, display scan electrode groups, address electrode groups, and the like are partially omitted for clarity.
  • the PDP 100 is composed of a front glass substrate 101 and a rear glass substrate 102.
  • N display electrodes 103 and N display scan electrodes 104 (the number is indicated when the N-th line is indicated) are formed.
  • 2 has M address electrodes 107 (the numbers are given when indicating the M-th electrode).
  • the front glass substrate 101 and the rear glass substrate 102 are sealed by a hermetic sealing layer 122 shown by oblique lines. It has an electrode matrix configuration of a three-electrode structure with each of the electrodes 103, 104, and 107, and a cell is formed at the intersection of the display scan electrode 104 and the address electrode 107. Further, a discharge space 122 is formed by the front glass substrate 101 and the rear glass substrate 102, and a display region 123 is formed.
  • the PDP 100 has a display electrode 103, a display scan electrode 104, a dielectric glass layer 105, and ⁇ [ ⁇ ⁇ on one main surface of a front glass substrate 101.
  • 0 R, 110 G, and 110 B are attached to the back panel, which is discharged into the discharge space 122 formed between the front panel and the back panel. This is a configuration in which electric gas is sealed.
  • the PDP 100 is connected to the PDP driving device 150 shown in FIG. 3 to constitute a plasma display device.
  • a display driver circuit 153, a display scan driver circuit 154, and an address driver circuit 155 are connected to each electrode of the PDP 100.
  • a voltage is applied to the display scan electrode 104 and the address electrode 107 in the cell to be turned on, and an address discharge is performed between them.
  • a sustain voltage is applied by applying a pulse voltage between the display scan electrodes 104. Due to the sustain discharge, ultraviolet rays are generated in the cells, and the cells are turned on by the emission of the phosphor layer excited by the ultraviolet rays. An image is displayed by a combination of lighting and non-lighting of each color cell. .
  • the front panel is composed of N display electrodes 103 and display scan electrodes 104 (only two electrodes are shown in FIG. 2) alternately and in parallel on the front glass substrate 101. After being formed in a stripe shape, the electrode is covered with a dielectric glass layer 105, and a MgO protective layer 106 is formed on the surface of the dielectric glass layer 105.
  • the display electrode 103 and the display scan electrode 104 are electrodes made of silver, and are formed by applying a silver paste for an electrode by screen printing and then firing.
  • the dielectric glass layer 105 should be baked at a predetermined temperature for a predetermined time, for example, 560 ° C for 20 minutes after applying a base containing a lead oxide or zinc oxide glass material by screen printing. Is formed so as to have a predetermined layer thickness (about 20 m).
  • the paste containing a glass material of the lead-based for example, P B_ ⁇ (7 0 wt), B 2 0 3 (1 5 wt%), S i 0 2 (1 0 wt%), and A 1 2 0 3 (5 wt%) and organic binder ( ⁇ _terpineol with 10%
  • the organic binder is obtained by dissolving a resin in an organic solvent.
  • the Mg ⁇ protective layer 106 is made of magnesium oxide (Mg0).
  • the layer has a predetermined thickness (approximately 0. 0) by a sputtering method or a CVD method (chemical vapor deposition method). 5 ⁇ m).
  • the rear panel is first formed by screen-printing silver paste for an electrode on the rear glass substrate 102 and then baking it to form M address electrodes 107 in a row.
  • a paste containing a lead oxide-based or zinc oxide-based glass material is applied thereon by a screen printing method to form a dielectric glass layer 108, which also includes a lead oxide-based or zinc oxide-based glass material.
  • the partition walls 109 are formed. By the partition walls 109, the discharge space 122 is divided into one cell (unit light emitting area) in the line direction.
  • FIG. 4 is a cross-sectional view of the PDP 100.
  • the gap dimension W of the partition wall 109 is set to a fixed value, for example, about 130 m to 240 m in the case of an HD-TV of 32 inches to 50 inches.
  • a yttrium oxide-based red phosphor (R) phosphor layer whose surface is positively (+)-charged as a red phosphor layer 110R is provided.
  • green phosphor layer 1 1 0 G, MMG surface are positively (+) charged
  • _ x A 1 ,, 0 19 a green phosphor of Aruminei preparative system containing aluminum Mn, also having a positive (+) charge (Y Gdx) BO 3:.
  • Each of these phosphor layers is formed by applying each phosphor phosphor in the form of a paste with an organic binder to each of the phosphor particles in a partition wall, and sintering them at a temperature of about 500 ° C. to form an organic binder.
  • phosphor layers 110 R, 110 G, and 110 B formed by binding the respective phosphor particles.
  • the thickness L of the phosphor layers 110 R, 110 G, and 110 B in the stacking direction on the address electrodes 107 is formed to be about 8 to 25 times the average particle size of the phosphor particles of each color. It is desirable to do.
  • the phosphor particles in order to secure the luminance (luminous efficiency) when the phosphor layer is irradiated with a certain amount of ultraviolet light, should have a thickness of at least 8 layers, preferably about 20 layers. Is desirable. If the thickness is larger than this, the luminous efficiency of the phosphor layer is almost saturated, and the size of the discharge space 122 cannot be sufficiently secured.
  • the front panel and the rear panel manufactured in this manner are overlapped so that each electrode of the front panel and an address electrode of the rear panel are orthogonal to each other, and a sealing glass is interposed at the periphery of the panel. Is fired at, for example, about 450 ° C. for 15 minutes to form an air-tight sealing layer 121, thereby sealing. Their to temporarily discharge space 1 2 2 in a high vacuum, for example, 1.
  • FIG. 5 is a schematic configuration diagram of an ink coating device 200 used when forming the phosphor layers 110R, 110G, and 110B. As shown in FIG.
  • the ink application device 200 includes a server 210, a pressure pump 220, and a header 230, and is supplied from a server 210 that stores phosphor ink.
  • the phosphor ink is supplied under pressure to the header 230 by a pressure pump 220.
  • the header 230 is provided with an ink chamber 230a and a nozzle 240, and the pressurized phosphor ink supplied to the ink chamber 230a is continuously supplied from the nozzle 240. It is configured to be discharged to
  • the diameter D of the nozzle 240 is 30 m or more to prevent clogging of the nozzle, and the distance W between the partition walls 109 (approximately 130) to prevent protrusion from the partition wall during coating. ⁇ ! ⁇ 200m) It is desirable to set it to the following or less, and it is usually set to 30m ⁇ 130m.
  • the header 230 is configured to be linearly driven by a header scanning mechanism (not shown), and scans the header 230 and continuously discharges the phosphor ink 250 from the nozzles 240. By doing so, the phosphor ink is uniformly applied to the grooves between the partition walls 109 on the rear glass substrate 102.
  • the viscosity of the phosphor used is kept in the range of 150 to 500 000 CP at 25 ° C.
  • the server 210 is provided with a stirrer (not shown), and the stirring prevents precipitation of particles in the phosphor ink.
  • the header 230 is integrally formed including the portions of the ink chamber 230a and the nozzle 240, and is manufactured by machining and electric discharge machining of a metal material. '
  • the method of forming the phosphor layer is not limited to the above method, and various methods such as a photolithography method, a screen printing method, and a method of disposing a film in which phosphor particles are mixed are used. can do.
  • the phosphor ink is prepared by mixing phosphor particles of each color, a binder, and a solvent so as to have a viscosity of 150 to 5,000 centipoise (CP). Agents, silica, dispersants (0.1-5 wt%) and the like may be added.
  • the phosphor red phosphor is formulated inks, (Y, Gd) wBOg: E u x or Y 2 _ x 0 3,: preferred compounds to be used represented by E u x.
  • These are compounds in which a part of the Y element constituting the base material is replaced by Eu.
  • the substitution amount X of the Eu element with respect to the Y element is preferably in the range of 0.05 ⁇ X ⁇ 0.20. If the replacement amount is larger than this, it is considered that the luminance becomes high but the luminance deteriorates remarkably, so that practical use becomes difficult.
  • the substitution amount is less than this, the composition ratio of Eu, which is the emission center, decreases, and the luminance decreases, so that it cannot be used as a phosphor.
  • the green phosphor MMg, — X A 1 ⁇ ⁇ 19 : Mn x (where M is Ce, La, and preferably x) range, 0.0) or the yttria-based (Y y Gd a) B0 3 :.
  • C e x the compound represented by T b x and mixed (yttria systems of these phosphors may be one or more) is used
  • the substitution amount of A 1 for G a, the substitution amount of G d for Y, the substitution amount of G d for Y, and the substitution amount y of T b for Y are 0. l ⁇ x ⁇ l. 0, 0 ⁇ a ⁇ 0, respectively. 9, 0.0 2 ⁇ y ⁇ 0.4
  • the substitution amount of C e and D 13 to Mg be 0.01 ⁇ x ⁇ 0.1.
  • E u x is, B a constituting the host material A compound in which some of the elements are replaced by Eu or Sr.
  • the substitution amount X of the Eu element with respect to the Ba element is desirably 0.03 ⁇ X ⁇ 0.2
  • y is desirably in the range of 0.1 ⁇ y ⁇ 0.5.
  • Acrylic resin is used as the binder to be mixed with the phosphor ink (0.1 to 0.5% of the ink is mixed). Can be used.
  • a polymer such as ⁇ or ⁇ VA can be used as a binder, and an organic solvent such as diethylene glycol or methyl ether can be used as a solvent.
  • phosphor particles produced by a solid phase firing method, an aqueous solution method, a spray firing method, or a hydrothermal synthesis method are used. Next, the production of these phosphor particles will be described.
  • the mixed solution preparing step as a raw material, barium nitrate B a (N0 3) 2, magnesium nitrate Mg (N_ ⁇ 3) 2, aluminum nitrate A 1 (N0 3) 3, nitric acid europium E u (N0 3 ) 2 is mixed so that the molar ratio becomes 1— X: 1: 10: X (0.03 ⁇ X ⁇ 0.25), and this is dissolved in an aqueous medium to prepare a hydrated liquid mixture. I do.
  • This aqueous medium is preferably ion-exchanged water or pure water because it does not contain impurities, but can be used even if these contain a non-aqueous solvent (methanol, ethanol, etc.).
  • the hydrated mixture is placed in a container made of a material having corrosion resistance and heat resistance such as gold or platinum, and is heated to a predetermined temperature in a high-pressure container using a device that can be heated while applying pressure, such as an autoclave. (100 to 300 ° C) and hydrothermal synthesis (12 to 20 hours) under a specified pressure (0.2 to LOMPa).
  • this powder is fired under a reducing atmosphere (for example, an atmosphere containing 5% of hydrogen and 95% of nitrogen) at a predetermined temperature and for a predetermined time (for example, 2 hours at 135 ° C.).
  • desired blue phosphor B a by classifying them, X M g a 1 10 O 17:. £ ⁇ can be obtained.
  • annealing in oxygen-nitrogen at 700 to 100 ° C converts one part of Eu into trivalent to trivalent. Process to remove oxygen vacancies.
  • a blue phosphor can also be produced by a spraying method in which the hydrated mixture is sprayed from a nozzle into a high-temperature furnace to synthesize a phosphor.
  • B a, _ x _ y S r y M g A 1 10 O 17 describes blue phosphor E u x.
  • the raw materials used will be described. Barium hydroxide Ba (OH) 2 , strontium hydroxide Sr (OH) 2 , magnesium hydroxide Mg (OH) 2 , aluminum hydroxide A 1 (OH) 3 , europium hydroxide Eu (OH) 2 is weighed to the required molar ratio.
  • an average particle diameter of the phosphor particles is about 0.1 to 3.0 ⁇ 1 m.
  • this is calcined at a predetermined temperature of 100 to 160 ° C. for 2 hours in a reducing atmosphere of, for example, 5% hydrogen and 95% nitrogen, and then classified by an air classifier to obtain a phosphor powder. Is prepared.
  • this in order to eliminate the adsorption site of water and hydrocarbon gases, this is annealed at 700 to 100 ° C in oxygen and nitrogen to convert one part of the divalent Eu into trivalent. Remove oxygen vacancies.
  • Oxides, nitrates, and hydroxides were mainly used as raw materials for the phosphor, but organometallic compounds containing elements such as Ba, Sr, Mg, Al, and Eu, such as metal oxides, were used.
  • Phosphors can also be prepared using lucoxide, acetylacetone, or the like.
  • a light-emitting substance Mn in order to replace the Mg, the formula is (are ⁇ L a, C e) M (Mg ,. x Mn x) A 1 ⁇ 0 19 are describe.
  • lanthanum oxide L a 2 0 3, cerium oxide C e 2 ⁇ 3, magnesium oxide Mg O, aluminum oxide A 1 2 ⁇ 3 and manganese carbonate Mn is a light-emitting substance the C0 3, the composition of M (Mg, _ x Mn x ) such that a 1 " ⁇ 19, formulated determined and the molar ratios of oxides as necessary, the value of X, then a small amount
  • the mixture of these fluxes (A 1 F 3 , NH 4 F) is mixed with these fluxes, and then calcined in air at 950 to 130 ° C. for 2 hours.
  • annealing is performed at 500 to 900 ° C. in oxygen or oxygen-nitrogen to remove oxygen vacancies and produce a positively charged green phosphor.
  • yttrium oxide as a raw material (Y 2 0 3), gadolinium oxide (G d 2 0 3), gallium oxide (G a 2 0 3), aluminum oxide (a 1 2 0 3), boron oxide (B 2 0 3), and a light-emitting substance is a terbium oxide and (T b 2 ⁇ 3) were blended according to the composition of each phosphor After mixing with a small amount of flux, the mixture is fired in air at 900 to 130 ° C. for 4 hours.
  • the raw materials yttrium nitrate Y 2 ( ⁇ 3 ) 3 , water gadolinium nitrate G d 2 (N 0 3 ) 3 , boric acid H 3 B 0 3 and europium nitrate E u 2 (N 0 3 ) 3
  • the molar ratio is 1 _X: 2: X (0.05 ⁇ X ⁇ 0.20) (the ratio of Y to Gd is 65:35).
  • this is heat-treated in air at 1200 to 135 ° C. for 2 hours, and then classified to obtain a red phosphor. Since red is fired in air, there is relatively little oxygen deficiency without annealing in oxygen-nitrogen, but defects may occur in the classification step, and anneal is preferred.
  • a raw material a mixture of yttrium nitrate Y 2 ( ⁇ 0 3) 3 and europium nitrate E u 2 (N0 3) 3 , molar ratio of 2 -X: X (0. 0 5 ⁇ X ⁇ 0.30) to prepare a mixed solution by dissolving in ion-exchanged water.
  • a basic aqueous solution such as an aqueous ammonia solution is added to the aqueous solution to form a hydrate.
  • the hydrate and ion-exchanged water are placed in a container made of a corrosion-resistant and heat-resistant material such as platinum or gold.
  • Hydrothermal synthesis is carried out for 3 to 12 hours under the conditions of 0 to 300 ° C and a pressure of 0.2 to 0.2 MPa. Thereafter, drying of the obtained compound, the desired Y 2 _ x ⁇ 3: E u x is obtained.
  • this phosphor is annealed in air at 130 ° C. to 1400 ° C. for 2 hours and then classified to obtain a red phosphor.
  • the phosphor obtained by this hydrothermal synthesis step is The particle size is about 0.1 to 2.0 zm and its shape is spherical. This particle size and shape are suitable for forming a phosphor layer having excellent light emission characteristics.
  • these red phosphors are fired in air, there are few oxygen defects, and therefore, little adsorption of water and hydrocarbon gases.
  • M (M g! _ X Mn x ) A 1 ⁇ 0 19 ( ⁇ represents any one of La and Ce) ) has a green phosphor Al Min acid salt, the same positive (+) charge of ( ⁇ , - x Gd x) BO 3: Tb, (Y WINCH X G d x) a 1 3 ( B_ ⁇ 3) 4: T b, (Y have X G d x) A 1 3 ( B_ ⁇ 3) 4: C e, T b, Y 3 A 1 3 G a 2 0 12: T b, L a M g, _ X a 1 n 0 19: C e x, is used green phosphor Itsutoria containing T b x.
  • the conventional Z n 2 S I_ ⁇ 4: Mn green phosphor since the negatively charged, clogging of nozzles tends to occur in the phosphor step, also the luminance when light is emitted green drops There was a tendency.
  • the green phosphor of the present invention when used, nozzle clogging during the phosphor coating process is prevented, color shift and luminance degradation of the panel and address discharge error are prevented, and luminance of white display is improved. Can be.
  • a phosphor sample based on the above embodiment was prepared, and a PDP using the sample was applied to a plasma display device, and a performance evaluation experiment was performed.
  • Each fabricated plasma display device has a size of 42 inches (HD-TV specification with a rib pitch of 150 m), a dielectric glass layer thickness of 20 m, and a Mg ⁇ protective layer thickness of 0.5. m, and the distance between the display electrode and the display scan electrode was 0.08 mm.
  • the discharge gas sealed in the discharge space is a gas containing a mixture of xenon gas of 5% to 90% mainly composed of neon, and sealed at a pressure of 66.5 KPa as the discharge gas. is there. Table 1 lists the combinations of phosphor samples used for each PDP.
  • the aluminate positively a static-as a green phosphor M (M g, _ x Mn x A 1 n 0 19 (where, L a, any one of the C e) and yttria-based (Y, + y G d b ) (G a, _ x a 1 x) (BO 3) 4:.
  • the phosphor particles used in Sample 1 1 PD P any one of the positively charged aluminate system which M (M g Bok x Mn x A 1 u 0 19 (although, L a, C e ) and magnet plum byte system L aMg t _ x a 1 n 0 19: C e x, a mixed phosphor of the green phosphor of T b x, (B a, S r) M g a 1,.
  • the green phosphor used for the sample 14-1 9 as a comparative example a conventional negative (1) charging Z n 2 S I_ ⁇ 4: Mn, the i3- alumina crystal B a A 1 12 ⁇ 17: Mn, B aMg a 1 14 0 23: E u, Mn, phosphoric acid of L a P 0 4: is used any one enters phosphor of the T b.
  • B aMg A 1 10 O 17 E u for blue phosphor
  • B 0 3 Using each of the E u. Table 1 shows the composition of each phosphor.
  • Phosphor in the prepared panel blue, green, red
  • water, co the adsorption amount of co 2 or hydrocarbons was measured by TD S (Atsushi Nobori mass spectrometry).
  • TD S Adsushi Nobori mass spectrometry
  • 100 milligrams (mg) of the phosphor in the prepared panel was collected, and the temperature was raised from room temperature to 600 ° C, and the total amount of water and hydrocarbon-based gas emitted was measured.
  • the amounts of water and hydrocarbon-based gas in Sample 1 were normalized to 1, and the amounts of water and hydrocarbon-based gas in Samples 2 to 19 were relatively compared.
  • the luminance (all white, green, blue, and red) and color temperature of the panel after the panel manufacturing process were measured using a luminance meter.
  • Table 2 shows the results of these experiments 1 to 4 for the luminance of green, the rate of change in luminance degradation, and the presence or absence of addressless errors.
  • the green phosphors of Comparative Samples 14 to 19 are as follows: Sample 1 is a combination of Zn 2 Si 4 : Mn and. (Y, Gd) B 3 : Tb. Le 1 5 B a A 1 12 0 19: Mn and (Y, G d) a combination of B_ ⁇ 3, samples 1 6 Z n 2 S i 0 4: Mn only, sample 1 7 B AMG A 1 14 0 23: E u, Mn only, sample 1 8 B a a 1 12 O ig: Mn only, sample 1 9 B a a 1 12 0 17: Mn and L a P 0 4: a combination of T b blue phosphor B a S r M g a 1 10 O 17: a sample using E u.
  • the adsorption of water is 2 to 3 times as large as that of the embodiment of the present invention, and the absolute amount is 1/5 to 1 Z10, but the amount of hydrocarbon gas is also 2 to 3 times as large. ing.
  • the green, blue, and red combination panels of Samples 1 to 13 all have a low rate of change in the luminance of each color due to ultraviolet light (147 nm) or a sustain discharge pulse, resulting in a decrease in color temperature. No nozzle clogging at the time.
  • a magnetoplumbite crystal structure containing A 1 ⁇ ! (3 ⁇ 448 1 _: ( 11 ) ( ) AluOw or , containing Y or a 1 ( ⁇ , + yGdb) (G a ⁇ a lx) 3 (B0 3) 4: Tb y, (Y ,.
  • the charge state of each color phosphor crystal is made positive, and in particular, A 1 and Y having a relatively large electron emission coefficient with little adsorption of moisture and hydrocarbons on the green phosphor are used as the matrix. Even if the Xe partial pressure in the panel is high, the green phosphor is composed of aluminate-based or yttria-based phosphor particles having a magnetoplumbite crystal structure. This is useful for a large-screen display device or the like because a highly reliable panel free from a drop in luminance and color temperature and free from address mistakes can be realized.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Luminescent Compositions (AREA)
  • Gas-Filled Discharge Tubes (AREA)

Abstract

L'invention concerne un écran plasma dans lequel toutes les charges sont positives. Cet écran contient un phosphore vert qui réagit à peine avec l'eau, le monoxyde de carbone, un gaz de dioxyde de carbone ou un hydrocarbure, ou qui les absorbe à peine. Pour le phosphore vert, on utilise une combinaison de phosphore vert MMg1-xAl11O19 :Mnx (M représentant La ou Ce) présentant une structure cristalline de magnétoplombite, et de phosphore vert à base de borate d'yttrium ou d'aluminate d'yttrium constitué d'un matériau représenté par la formule générale (Y1-a-yGda)BO3:Tby ; par la formule générale (Y1-a-yGda)(Ga1-xAlx)3(BO3)4 :TBy ; ou par la formule générale (Y1-a-yGda)(Ga1-xAlx)3(BO3)4 :Cey, Tby, (Y1-y)3(Ga1-xAlx)5O12 :Tby, LaMg1-xAl11O19 :Cex, Tbx.
PCT/JP2004/009483 2003-06-30 2004-06-29 Ecran plasma WO2005001873A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP04746952A EP1655757A4 (fr) 2003-06-30 2004-06-29 Ecran plasma
US10/534,398 US7268492B2 (en) 2003-06-30 2004-06-29 Plasma display device with green emitting phosphor that becomes positively charged
CN2004800017914A CN1723522B (zh) 2003-06-30 2004-06-29 等离子体显示装置

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JP2003186837A JP4415578B2 (ja) 2003-06-30 2003-06-30 プラズマディスプレイ装置
JP2003-186837 2003-06-30

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CN (1) CN1723522B (fr)
WO (1) WO2005001873A1 (fr)

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CN104178163A (zh) * 2013-05-23 2014-12-03 海洋王照明科技股份有限公司 铈铽共掺杂稀土硼镓酸盐的发光薄膜及其制备方法和电致发光器件
US10947503B2 (en) 2014-12-25 2021-03-16 International Institute Of Cancer Immunology, Inc. Method for modifying T cell population
US10259716B2 (en) * 2016-09-16 2019-04-16 General Electric Company Boron doped rare earth metal oxide compound
WO2021120021A1 (fr) * 2019-12-17 2021-06-24 深圳市大富科技股份有限公司 Matériau céramique et son procédé de préparation
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KR20050095598A (ko) 2005-09-29
CN1723522B (zh) 2010-09-29
EP1655757A4 (fr) 2010-01-27
JP2005025958A (ja) 2005-01-27
CN1723522A (zh) 2006-01-18
US7268492B2 (en) 2007-09-11
EP1655757A1 (fr) 2006-05-10
US20060017385A1 (en) 2006-01-26
KR100742453B1 (ko) 2007-07-25

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